2-胺基-1,3,4-噻二唑衍生物之合成｜國立中央大學博碩士論文系統

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研究生：	范俊義 Chun-Yi Fan
論文名稱：	2-胺基-1,3,4-噻二唑衍生物之合成 Synthesis and characteristics of 2-amino-1,3,4-thiadiazole derivatives
指導教授：	郭坤土 Kung-Tu Kuo
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
畢業學年度：	93
語文別：	中文
論文頁數：	79
中文關鍵詞：	噻二唑、吖次甲基染料、偶氮染料
外文關鍵詞：	thiadiazole, azamethine dyes, azo dyes
相關次數：	點閱：12 下載：0
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本研究即合成一系列2-胺基-1,3,4-噻二唑類化合物，產率為32~94%，合成條件為胺基硫尿：
(1)與芳香族(或雜環)甲酸於三氯氧化磷中加熱迴流可得7種(Ⅰa~Ⅰe、Ⅱa~Ⅱb)
(2)與異尼古丁酸反應時使用聚磷酸為脫水縮合劑環化為2-胺基-5-(4-吡啶基)-1,3,4-噻二唑(Ⅰf)
(3)與甲酸反應則使用濃鹽酸即可得2-胺基-1,3,4-噻二唑(Ⅰg)
(4)與苯甲醛先縮合為1-苯基硫卡半腙(Ⅲ)經氯化鐵之氧化與環化成2-胺基-5-苯基-1,3,4-噻二唑(Ⅰa)
並且以此類化合物為原料與R酸、2-萘酚及N,N-二甲基苯胺合成一些偶氮(N=N)染料，與4-二甲胺基苯甲醛合成吖次甲基(C=N)染料。將所合成之1,3,4-噻二唑系染料與苯系染料比較，觀察其可見光譜之最大吸收波長差異，所得結果顯示1,3,4-噻二唑環確實有達到紅位移效果。在R酸偶氮染料中，1,3,4-噻二唑系染料相較苯系染料於鹼性水溶液中UVλmax紅位移了9~59nm，在2-萘酚偶氮染料中，乙醇溶液加鹼條件下為53~75nm，N,N-二甲基苯胺偶氮染料中，乙醇溶液中則為86~107nm。而在吖次甲基染料中，亦再度顯示雜環具此項特性，波長差距66nm。合成之1,3,4-噻二唑吖次甲基染料意外觀察到Ⅸa與Ⅸd固體具有強螢光性質，溶於DMF中測得最大螢光放射波長分別為524、540nm。

A series of 2-Amino-1,3,4-thiodazole has been synthesized which exhibit various yields of 32~94%. The reaction conditions were that thio-
semicarbazide:
(1) and aromatic(or heterocyclic)acid were put into Phosphorus oxy-
chloride (POCl3), then were heated and refluxed, seven kinds of Ⅰa ~
Ⅰe, Ⅱa~Ⅱb can be obtained.
(2) reacted with isonicotinic acid and cyclodehydration by Poly-
phosphoric acid (PPA). 2-amino-5-(4-pyridyl)-1,3,4-thiadiazole(Ⅰf)
was obtained.
(3) reacted with formic acid in concentrated hydrochloride, 2-amino-
1,3,4-thiadiazole(Ⅰg) can be obtained.
(4) and benzaldehyde were underwent condensation reaction to 1-phenyl-
thiosemicarbazone(Ⅲ). Then it was oxidized and cyclized by ferric
chloride to 2-amino-5-phenyl-1,3,4-thiadiazole(Ⅰa)
These 1,3,4-thiadiazole derivatives were taken as raw materials. then they were coupled with R-acid,2-naphthol and N,N-dimethylaniline to
synthesized some azo (N=N) dyes; condensed with 4-dimethylamino-
benzaldehyde to get azamethine(C=N) dyes. Compared and observed the difference between 1,3,4-thiadiazole’s dyestuffs and benzene’s dyestuffs there maximum of the absorptive wavelengths of the visible light, the result revealed that bathochromic shift effect was occurred when
1,3,4-thiadiazole ring existence.
In R-acid azo dyes , the UVλmax was bathochromic shifted 9~59 nm in 1,3,4-thiadiazole dyes than in azobenzene dyes under basic solution. Under basic ethanol solution, the difference of UVλmax is 53~75 nm in 2-naphthol azo dyes; Under ethanol solution, 86~107nm in N,N-dimethylaniline azo dyes. It exhibited similar characteristic again in azamethine dyestuff. And the difference of UVλmax is 66nm.
Unexpectedly, strong fluorescence can be observed in Ⅸa and Ⅸd of 1,3,4-thiadiazole azamethine dyes. The maximum emission Fluore-
Scence of wavelength is 524 and 540nm, respectively.

摘要--------------------------------------------------------------------------------Ⅰ
Abstract --------------------------------------------------------------------------Ⅱ
目錄--------------------------------------------------------------------------------Ⅳ
圖目錄-----------------------------------------------------------------------------Ⅶ
表目錄-----------------------------------------------------------------------------Ⅹ
第一章  緒論---------------------------------------------------------------------1
第二章	文獻回顧-----------------------------------------------------------------3
第三章	實驗部分---------------------------------------------------------------10
1  實驗儀器、藥品-----------------------------------------------------------10
1.1實驗儀器-------------------------------------------------------------------10
1.2實驗儀器之操作----------------------------------------------------------10
1.3實驗藥品-------------------------------------------------------------------11
2實驗流程---------------------------------------------------------------------14
2.1  2-胺基-1,3,4-噻二唑類化合物之反應流程------------------------14
2.2  R酸偶合之偶氮染料反應流程---------------------------------------15
2.3  重氮鹽製備流程--------------------------------------------------------15
2.4  2-萘酚偶合之偶氮染料反應流程---------------------------------- 16
2.5  N,N-二甲基苯胺偶合之偶氮染料反應流程---------------------- 16
2.6  4-二甲胺基苯甲醛縮合之吖次甲基染料反應流程------------- 17
3  2-胺基-1,3,4-噻二唑類化合物之合成--------------------------------18
3.1  2-胺基-5-苯基-1,3,4-噻二唑之合成(Ⅰa)--------------------------18
3.1.1  1-苯基硫半卡腙中間體之合成(Ⅲ)-------------------------------18
3.1.2  1-苯基硫半卡腙中間體(Ⅲ)氧化成2-胺基-5-苯基-1,3,4-噻二
唑(Ⅰa)之合成-------------------------------------------------------19
3.2  2-胺基-5-(4-硝基苯基)-1,3,4-噻二唑之合成(Ⅰb)---------------19
3.3  2-胺基-5-呋喃基-1,3,4-噻二唑之合成(Ⅰc)-----------------------19
3.4  2-胺基-5-噻嗯基-1,3,4-噻二唑之合成(Ⅰd)-----------------------20
3.5  2-胺基-5-(4-二甲胺苯基)-1,3,4-噻二唑之合成(Ⅰe)-------------20
3.6  2-胺基-5-(4-對吡啶基)-1,3,4-噻二唑之合成(Ⅰf)----------------21
3.6.1  4-吡啶-羰基硫半卡肼中間體之合成(Ⅳ)------------------------21
3.6.2  4-吡啶-羰基硫半卡肼中間體(Ⅳ)環化成2-胺基-5-(4-吡啶基)-1,3,4-噻二唑(Ⅰf)之合成--------------------------------------22
3.7  2-胺基-1,3,4-噻二唑之合成(Ⅰg)------------------------------------22
3.8  5,5’-間-伸苯基-雙-2-胺基-1,3,4-噻二唑之合成(Ⅱa)------------22
3.9  5,5’-對-伸苯基-雙-2-胺基-1,3,4-噻二唑之合成(Ⅱb)------------23
3.9.1  1,1’-對苯二甲醯硫半卡肼中間體之合成(Ⅴ)------------------ 23
3.9.2  1,1’-對苯二甲醯硫半卡肼中間體(Ⅴ)環化成5,5’-對-伸苯基-雙-2-胺基-1,3,4-噻二唑之合成(Ⅱb)---------------------------- 24
3.10  2-胺基-5-苯基-1,3,4-噻二唑乙醯化(Ⅰa-Ac)及水解反應-----24
4  R酸之偶氮染料合成----------------------------------------------------25
4.1  2-羥基-1-(5-苯基-1,3,4-噻二唑-2-偶氮)伸萘基-3,6-二磺酸之合成(Ⅵa)-------------------------------------------------------------------25
4.2  2-羥基-1-(5-(4-硝基苯基)-1,3,4-噻二唑-2-偶氮)伸萘基-3,6-二磺酸(Ⅵb)----------------------------------------------------------------26
4.3  2-羥基-1-(1,3,4-噻二唑-2-偶氮)伸萘基-3,6-二磺酸(Ⅵc)-------26
4.4  2-羥基-1-(苯偶氮)伸萘基-3,6-二磺酸之合成(Ⅵd)--------------26
4.5  2-羥基-1-(4-硝基苯偶氮)伸萘基-3,6-二磺酸之合(Ⅵe)---------27
5  2-萘酚之偶氮染料合成-------------------------------------------------28
5.1  1-(5-苯基-1,3,4-噻二唑-2-偶氮)-2-萘酚之合成(Ⅶa)------------28
5.2  1-(1,3,4-噻二唑-2-偶氮)-2-萘酚之合成(Ⅶb)---------------------28
5.3  1-苯偶氮-2-萘酚之合成(Ⅶc)----------------------------------------29
6  N,N-二甲基苯胺之偶氮染料合成-------------------------------------29
6.1  4-(5-苯基-1,3,4-噻二唑-2-偶氮)-N,N-二甲基苯胺之合成(Ⅷa)--------------------------------------------------------------------------29
6.2  4-(1,3,4-噻二唑-2-偶氮)-N,N-二甲基苯胺之合成(Ⅷb)---------30
6.3  對二甲胺基偶氮苯之合成(Ⅷc)-------------------------------------31
7  4-二甲胺基苯甲醛之吖次甲基染料合成----------------------------31
7.1  2-(4-(N,N-二甲胺基)苯亞甲基胺)-5-苯基-1,3,4-噻二唑之合成(Ⅸa)----------------------------------------------------------------------31
7.2  其它次吖甲基染料之合成--------------------------------------------32
第四章  結果與討論-----------------------------------------------------------33
1 原料合成之結果-----------------------------------------------------------33
2  2-胺基-1,3,4-噻二唑類化合物合成判定方法-----------------------34
3  2-胺基-5-苯基-1,3,4-噻二唑化合物合成之探討--------------------35
4  2-胺基-5-(4-吡啶基)-1,3,4-噻二唑化合物合成之探討------------36
5  2-胺基-5-苯基1,3,4-噻二唑之乙醯化及水解反應之探討--------36
6  R酸偶合之偶氮染料合成結果與探討-------------------------------37
7  2-萘酚偶合之偶氮染料合成結果與探討----------------------------39
8  N,N-二甲基苯胺之偶氮染料合成結果與討論----------------------39
9  吖次甲基染料之合成結果與探討-------------------------------------40
10  偶氮染料與次甲基胺染料之可見光最大吸收波長比較--------42
第五章  結論--------------------------------------------------------------------43
第六章	參考文獻-------------------------------------------------------------44
附圖--------------------------------------------------------------------------------46

                                

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